Forming synthetic material with glyceryl trimontanate as a lubricant

ABSTRACT

Glyceryl trimontanate has excellent lubricating properties which are displayed upon its addition as an auxiliary agent to the reactive mixture for a synthetic plastic material; the resultant synthetic material is more easily formed such as by extrusion, and has improved shock resistance and transparency.

United States Patent [1 1 [111 3,864,295 Boussely Feb. 4, 1975 FORMING SYNTHETIC MATERIAL WITH [56] References Cited GLYCERYL TRIMONTANATE AS A UNITED STATES PATENTS LUBRICANT 3,442,837 5/1969 Brotz et al. 264/300 [75] Inventor: Jean Boussely, Paris, France [73] Assignee: Societe Sapchim-Fournier-Cimag, Primary Examiner-Allan Lieberman Paris, France Attorney, Agent, or Fzrm-Young and Thompson [22] Filed: Mar. 11, 1974 ABSTRACT [2]] Appl 450085 Glyceryl trimontanate has excellent lubricating properties which are displayed upon its addition as an aux- [52] US. Cl... 260/28.5 D, 260/285 A, 260/285 R, iliary agent to the reactive mixture for a synthetic 260/316, 264/300 plastic material; the resultant synthetic material is [51] Int. Cl..... C08f 45/36, C08f 45/52, ClOm 3/20 more easily formed such as by extrusion, and has im- [58] Field of Search..... 260/285 A, 28.5 D, 28.5 R, proved shock resistance and transparency.

8 Claims, N0 Drawings FORMING SYNTHETIC MATERIAL WITH GLYCERYL TRIMONTANATE AS A LUBRICANT This is a continuation of application Ser. No. 250,002, filed May 3, 1972 and now abandoned. Application Ser. No. 250,002 is a division of application Ser. No. 34,642 filed May 4, 1970 and now US. Pat. No. 3,691,219 granted Sept. 12, 1972.

The present invention relates to forming masses of synthetic material with the use as a lubricant of gylceryl trimontanate which corresponds to the following general formula:

in which R represents a linearly saturated hydrocarbon chain having 28 carbon atoms and includes products in which the linearly saturated hydrocarbon chain includes 24 to 32 carbon atoms.

The present invention also concerns a process for the preparation of glyceryl trimontanate.

This process comprises, in a general manner, esterifying montanic acid with glyceryl.

Preferably, this esterification corresponds to the following reaction equation:

' I'IO -C H 3 R COO H HO- -H R (100- 4-1 R COO- -H 3 H 0 R COO- -H This reaction is carried out directly without any solvant and at a temperature taking account of the pressure so that the water formed is water vapour. The 'reaction can thus be nearly if not totally carried to completion by the continuous shifting of the balance of the reaction in favour of the formation of the glyceryl trimontanate.

Moreover, in a general manner the kinetics of the reaction can be controlled by the quantity of distilled water as well as by the variation of certain common characteristics of any medium such as the acid number and/or the hydroxyl number.

Preferably, the esterification is carried out in the presence of a catalyst which will speed up the reaction. This catalyst may be an acid catalyst, such as B-naphthalene sulfonic acid; an alkaline catalyst, such as sodium or sodium methylate; a metallic catalyst, such as zinc powder; or any other suitable catalyst.

In practice the quantity of the catalyst which is used is very small; with regard to a catalyst soluble in glyceryl trimontanate, such a catalyst can remain in the final product without in any way affecting the characteristics of the final product other than possibly its colour; and with regard to an alkaline catalyst, its acid number. However, with regard to a catalyst which is insoluble in glyceryl trimontanate such as zinc powder, such a catalyst has to be removed from the final product by filtration.

PREPARATION EXAMPLES A process for the preparation of glyceryl termontanate according to the invention will now be described in detail by way of examples as follows:

Primary materials.

montanic acid 398 g glycerol 29.6 g

-bon. In practice montanic acid is commercially available as a product for which the number of carbon atoms of the hydrocarbon chain varies between 24 and 32.

The analysis of montanic acid used had the following characteristics:

acid number (A.No.) l4] saponification number (S.No.) 150 melting point (m.p.) ash nil Similarly, the glyceryl used had the following characteristics:

molecular weight (mol. wt.) 92.09 refractive index (at 20 C) [.4729 density (at 20 C) 1.260 boiling point 290 C CATALYSTUSED 0.43 grams of commercially available B-naphthalene sulfonic acid was used as the catalysts and has the following characteristics:

molecular weight (mul. wt.)

melting point (m.p.)

MODE OF PREPARATION The glyceral is placed in an apparatus capable of being placed under a vacuum.

The montanic acid is added and then the B-naphthalene sulfonic acid.

Air is then removed from the apparatus as a current of nitrogen is circulated therein. Nitrogen or any other inert atmosphere is circulated herein in order to avoid any possible oxydation of the reactive medium which could give an undesirable colour to the final product. The circulation of the nitrogen is continued until the apparatus'is under vacuum as described hereinafter.

The reactive medium is kept in motion and is maintained for 5 hours at 200 C by the heat of the oil bath of the apparatus. The reactive medium become homogeneous towards -90 C and from C the water is collected.

By means of a vacuum pump the pressure in the apparatus is dropped to approximately 5 millibars in 0.25 hours.

At this pressure, the temperature is raised to 220 C in 1 hour while continuing to collect the distilled water. The pressure is so maintained until the acid number of the reactive medium is less than H) or preferably near 7 which requires approximately 3 hours.

The reaction is then nearly complete.

The ester thus formed is cooled to 150 C. The vacuum is stopped in the apparatus and the cooling is of the ester continued until the temperature reaches It will be noted that in all the cases the hydroxyl number of glyceryl trimontanate obtained in accordance with the process according to the invention is between 10 and I5, and the saponification number is relatively ll-l00 C. 5 high The esief in question y y tnmonmnaw, m tha In all the cases the final product obtained can if necform of a y p 0 essary be bleached for example by an ozidizing agent, The Syrup F C run across Plate m such a sodium chlorite, or hydrogen peroxide used in order to obtam a solid layer having a thickness of sev- Small amounts, or by a bleaching agent Such as decolor W izing carbon or active carbon.

This solid layer IS broken up and the fragments are ground forming a powder which is then sifted.

APPLICATIONS RESULTS it 100 Percent y 410 grams 0f g y y I5 Glyceryl trimontanate exhibits remarkable properties montanate are obtained having the following characas an auxiliary agent for masses of synthetic material teristics: which are to be formed by molding, extrusion or extrusion-blowing; in particular the following synthetic mab AN 8 terials polyvinyl chloride, vinyl copolymers, polystygg z 'g gg f g 48.5 rene, acrylic resins, methacrylic resins, acrylonitrileester number 136.5 butadiene-styrene (ABS), polyethylene, polypropylene gzg ggg zwg :g or any other synthetic material. molecular weight (mol. wt.) l280l290 Firstly, insofar as known, it is necessary to add a lubricating agent to the masses of synthetic material in 'order to retard as long as possible the sticking to the OTHER MODES OF PREPARATION surfaces of the means in which the material is formed. Other modes of preparing glyceryl trimontanate have It is known to use higher acid esters of polyalcohols been carried out in which the B-naphthalene sulfonic such as glyceryl trihydroxy stearate. acid has been substituted by one of the following cata- Glyceryl trimontanate according to the invention has lysts, given with the corresponding quantity of which remarkable qualities as a lubricating agent, far superior was sed; to those of lubricatin a ent alread known as is illusg g l trated by the various tests which follow. These tests d 43 were all conducted under the same conditions and conso rum g sodium methyl 43 g sisted of record ng the time that it took for a sheet of zinc powder .86 g synthetic material passed between cylinders heated to 1m F g 210 C to begin to stick to the cylinders:

The mode of operation remains the same and the results obtained comparable to those indicated above.

Other suitable catalysts could of course be used. The follow table gives other examples of preparation TEST I carried out starting with montanic acid from various composition Ohhesheeu sources. P.V.C. I00

In column A of the table is indicated the nature and A xiliary agent (adjuvant) 8 quantity in grams of the reactants used; in column B the 45 Efsggmg characteristics of the montanic acid used; and in col- Glycgl'yi trihydroxy stcarttte 2 e r cteristics of the l cer l montanate ob- Refill"? U01 C th chd a g y y The sheet began to stick at the end of 2 minutes. tamed.

Example A B No.

montanic acid 398.0 A. No. 141 A. No. 8.1 l glyceral 29.6 S. No. l S. No. 148.5

paratoluenesulfonic acid 0.4 OH.No. 20 OH.No. l2 .4

montanic acid 280.0 A. No. I50 A. No. l0.l ll glyceral 23.0 S. No. I615 S. No. I55.

caustic sodalyl (50%) 0.6 OH.No. 20 OH.No. l4.5 montanic acid 367.0 A. No. I53 A. No. 9.2 lll glyceral 29.7 S. No. 164 S. No. I48 paratoluenesulfonic 0.4 OH.No. 16 OH. No. 14 montanic acid 359.0 A.No. I56 A.No 10.4 IV glyceral 29.6 S.No. l S.No. I50

caustic sodalyl (50%) 0.8 OH.No. l5 OH.No. l3 montanic acid 260.0 A.No. I58 A.No. 9.7 V glyceral 22.0 S.No. I 73.5 S.No I50 caustic sodalyl (50%) 0.56 OH.NO 27 OH.NO l5 TEST ll TEST Vll Composition of the sheet: Composition of the sheet P.C. V 100 P.V.C. 100 Auxiliary agent (adyuvant) 8 5 Auxiliary agent (adjuvant) 8 Epoxy O l 2 Thio-organic tin compound a-phenyltndole 0.6 Glyceryl trihydroxy stearate l Glyceryl trimontanate 0.5 Glyceryl trimontanate l Glyceryl trihydroxy stearate 1.5 Result Result: The sheet began to stick at the end of 18 The sheet began to stick at the end of 12 minutes. minutes.

TEST Vlll TEST m Composition of the sheet Composition of the sheet: P'V'.C.' PV C 100 Auxiliary agent (ad uvant) uxiliaryl agent (adjuvant) g ggg'ggfi's 'ggw gsgg poxy or Result a-phenyllndole 0.8 v Glyceryl trimontanate 1 20 The sheet began to stick at the end of Glyceryl trihydroxy stearate l mmutes' Result: The sheet began to stick at the end of 20 minutes.

The result of Tests V-Vlll are comparable to those I of the preceding tests l-V.

It Should be {loted that Percentage of 'P y 25 Other test have also been carried out in replacing the was y mcreaseqfn Order to exlend the length glyceryl trihydroxy stearate by one or the other of the of mm of thermal stabllltyesters formed by reacting a polyalcohol such as mono-,

di-, or tri-ethylene glycol, mono-, or di-propylene glycol, butanediol, trimethylolpropane, glucoses, sac- TEST W charoses, pentaor di-pentaerythrite with a higher acid comprising more than 10 atoms of carbon with or withk f zjp of the Sheet '00 out double linking, with or without hydroxyl functions, i age", (adj-mm, 8 suchas the following acids: lauric myristic, palmitic, Epohxy olil d I .Y. stearlc, oleic, lmoleic, lmolenrc, belmtc, behenlc, phloo-p enyin 0e Glywy] "momma 2 rontc, vaccenrc and others. The tlme m which the sheet Rem"; began to stick was the same as hereinabove indicated.' The began the end In all the cases the lubricating action of the glyceryl trimontanate was not altered, while the lubricating action of the ester was substantially improved.

In this first series of tests, the usual lubricating agent 40 In practice, the mixture of the glyceryl trimontanae was Progresswe.ly replaced by glyceryl mmomanate and the other ester can vary between great limits becoming to the i tween 15 85 percent of glyceryl trimontanate by It IS seen that thts replacement results in a considerweight with respect to the total mixture able, m P the end of f the Other tests have also been a carried out in which the mater'al begms to F to h Cy m polyvinyl chloride was replaced by vinyl copolymers,

l advantageously Permits the from F to polystyrene, acrilic resins, metacrylic resins, acronitrylfive times the length of continuous service of cylinders e butadiene-styrene, polyethylene and polypropylene. before necessary 9 F f and clean These tests all confirmed excellent lubricating, anti- Olher tests were earned 9" m b' the a'phenylm sticking and anti-friction qualities of glyceryl trimontadole was replaced by thlo'orgamc compound as nate. Further, as this factor is particularly important follows: relative to the speed at which material can be extruded,

the presence of glyceryl trimontanate permits such TESTV plastic material to be extruded at a substantially increased speed without sticking. Composition of the sheet The fact that glyceryl trimontanate obtained accordzC- ing to the invention has a lower hydroxylnumber is conuxiliary agent (ad uvant) 8 Thio-organic tin compound 1.5 sidered to enhance its excellent lubricating quality. Gllaycerlyl trihydroxyl stearate 2 In all the tests described in detail hereinabove, the esu t: The sheet began to stick at the end of 3 minutes. pree.nce of an iiuxlhary agent or adJuvdn. the com position tested ts noted. Such a product IS introduced in a known manner into the mixture in order to modify the polymerization structure and thereby improve the TEST physical characteristics of the final product, and partic- Composition of he ShaeI ularly as regards to shock resistance. For example with mac. I00 regard toa mixture having a polyvinyl chloride base, "8 8 such as explained more particularly hereinabove, such Thlo-organtc tin compound L5 Glyceryl trihydroxy stearate 1.5 an auxiliary agent could for example be an acrylic or gg f t "lmomunflm derivative acronitryle-butadiene-styrene. The sheet began flick he and f 10 Further, the tests described hereinabove have shown mlnutes.

that glyceryl trimontanate, i.e., relative to the second important property of this product, has a tendancy when it is in such a mixture to improve the distribution and the compatibility in the polycondensation medium of the auxiliary agent. This results in a better homogeneity of the combination with the following consequences: elimination of fish-eye irregularities and improved uniformity in the ultimate colour of the prod- UCt.

Finally, the tests showed a third important property of glyceryl trimontanate, i.e., the transparency of the.

final product is substantially improved when such a product is colourless especially in the case where the initial mixture contains auxiliary agents. The transparency of the final product is improved with increasing amounts of glyceryl trimontanate up to 2 percent of the total mixture by weight.

Accordingly, the transparency of the final product used in Test [I was better than that used in Test l and the transparency of the product used in Test lll better than that of the product used in Tests l and Il. With regard to the transparency of the material used in Test lV, it is nearly perfectly transparent and ressembles a high quality glass.

The similar findings were made with regard to transparency of the material in the Tests V-Vlll.

Increasing the amount of glyceryl trimontanate beyond 2 percent of the total mixture by weight increases the time before which the material begins to stick to the cylinders but hardly has an effect on the transparency.

With regard to the transparency of the final product, the transparency of the glyceryl trimontanate is itself important and accordingly a catalyst was chosen for the preparation of the glyceryl trimontanate which would not adversely affect its high transparency.

Finally, the tests which have been carried out have also shown that the synthetic products obtained from mixtures lubricated with glyceryl trimontanate did not develop white lines when folded.

Further, owing to the fact that it is insoluable in water and it has a high melting point, the glyceryl trimontanate does not effect the taste of products which are stored in receptacles formed of a synthetic material which has been lubricated therewith.

' In the abovementioned tests, the amount of glyceryl trimontanate was most often limited to'2 percent by weight because of legislation in France which limits the amount to this percentage. In practice systematic tests have been carried out with success between 0.] and 3 percent of glyceryl trimontanate, these tests have confirmed the remarkable qualities of this product.

I claim:

1. A method of forming a mass of synthetic material selected from the group consisting of polyvinyl chloride and vinyl copolymer, comprising admixing with said material a small but effective amount of glyceryl trimontanate as a lubricant, and thereafter contacting said mass with a solid member to impart a desired form to said mass, said amount being effective to increase the time during which said mass can be in contact with said member without sticking to said member.

2. A method as claimed in claim 1, said amount being in excess of 0.1 percent by weight of the whole.

3. A method as claimed in claim 1, said amount being about 0.] to 3 percent by weight of the whole.

4. A method as claimed in claim 1, said amount being in excess of about 0.5 percent by weight of the whole.

5. A method as claimed in claim 1, said amount being about 0.5 to 2 percent by weight of the whole.

6. A method as claimed in claim 1, said synthetic material being polyvinyl chloride.

7. A method as claimed in claim 1, said glyceryl trimontanate having the formula in which R is a linearly saturated hydrocarbon chain having 24 to 32 carbon atoms.

8. A method as claimed in claim 7, said glyceryl trimontanate having a hydroxyl number between 10 and 15. 

1. A METHOD OF FORMING A MASS OF SYNTHETIC MATERIAL SELECTED FROM THE GROUP CONSISTING OF POLYVINYL CHLORIDE AND VINYL COPOLYMER, COMPRISING ADMIXING WITH SAID MATERIAL A SMALL BUT EFFECTIVE AMOUNT OF GLYCERL TRIMONTANATE AS A LUBRICANT, AND THEREAFTER CONTACTING SAID MASS, SAID AMOUNT BEING TO IMPART A DESIRED FORM TO SAID MASS, SAID AMOUNT BEING EFFECTIVE TO INCREASE THE TIME DURING WHICH SAID MASS CAN BE IN CONTACT WITH SAID MEMBER WITHOUT STICKING TO SAID MEMBER.
 2. A method as claimed in claim 1, said amount being in excess of 0.1 percent by weight of the whole.
 3. A method as claimed in claim 1, said amount being about 0.1 to 3 percent by weight of the whole.
 4. A method as claimed in claim 1, said amount being in excess of about 0.5 percent by weight of the whole.
 5. A method as claimed in claim 1, said amount being about 0.5 to 2 percent by weight of the whole.
 6. A method as claimed in claim 1, said synthetic material being polyvinyl chloride.
 7. A method as claimed in claim 1, said glyceryl trimoNtanate having the formula
 8. A method as claimed in claim 7, said glyceryl trimontanate having a hydroxyl number between 10 and
 15. 